全文获取类型
收费全文 | 125120篇 |
免费 | 1340篇 |
国内免费 | 461篇 |
专业分类
化学 | 68577篇 |
晶体学 | 2035篇 |
力学 | 4956篇 |
综合类 | 5篇 |
数学 | 12104篇 |
物理学 | 39244篇 |
出版年
2016年 | 1273篇 |
2015年 | 985篇 |
2014年 | 1321篇 |
2013年 | 4779篇 |
2012年 | 3381篇 |
2011年 | 4396篇 |
2010年 | 2743篇 |
2009年 | 2518篇 |
2008年 | 3929篇 |
2007年 | 3983篇 |
2006年 | 4042篇 |
2005年 | 3969篇 |
2004年 | 3458篇 |
2003年 | 3150篇 |
2002年 | 3057篇 |
2001年 | 3574篇 |
2000年 | 2675篇 |
1999年 | 2199篇 |
1998年 | 1891篇 |
1997年 | 1873篇 |
1996年 | 1803篇 |
1995年 | 1774篇 |
1994年 | 1548篇 |
1993年 | 1537篇 |
1992年 | 1755篇 |
1991年 | 1748篇 |
1990年 | 1677篇 |
1989年 | 1683篇 |
1988年 | 1686篇 |
1987年 | 1674篇 |
1986年 | 1587篇 |
1985年 | 2135篇 |
1984年 | 2264篇 |
1983年 | 1891篇 |
1982年 | 2212篇 |
1981年 | 2028篇 |
1980年 | 2073篇 |
1979年 | 2058篇 |
1978年 | 2186篇 |
1977年 | 2090篇 |
1976年 | 2115篇 |
1975年 | 2053篇 |
1974年 | 1895篇 |
1973年 | 2102篇 |
1972年 | 1282篇 |
1971年 | 975篇 |
1970年 | 912篇 |
1969年 | 923篇 |
1968年 | 1050篇 |
1967年 | 1101篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
Low molecular weight tri-podal biphenyl- and benzoate-type mesogens [C6H5C6H4O(CH2)5SiMe2CH2CH2SiMe2]3CH (4), [C11H23O(C6H4)2O(CH2)5SiMe2]3CH (5) and [MeOC6H4OC(O)C6H4O(CH2)5SiMe2]3CH (6) (C6H4 = 1,4-phenylene) were obtained, from branched silyl substituted methane precursors [CH2CH(Me)2Si]3CH (1) and (HMe2Si)3CH (2). The biphenyl-containing ones (4) and (5) were converted into terminal alkenes, which were subsequently hydrosilylated with poly(methylsiloxanes). The polymer derived from (5) exhibited mesomorphic properties. Such systems have the potential to significantly increase the density of liquid crystal rod-like structures in side chains of linear polymers (or dendritic liquid crystal polymers). 相似文献
972.
Uranium(VI) complexed with aluminon (3-[bis(3-carboxy-4-hydroxy-phenyl)methylene]-6-oxo-1,4-cyclohexadiene-1-carboxylic acid triammonium salt) was determined by adsorptive cathodic stripping voltammetry (ACSV) using a hanging mercury drop electrode. Trace uranium(VI) and zinc(II) can be simultaneously determined in a single scan in the presence of aluminon and urea. Optimal conditions were found to be: accumulation time; 180–200 s, accumulation potential; 50 mV versus Ag/AgCl, scan rate; 40 mV s−1, supporting electrolyte; 0.1 M sodium acetate buffer at pH 6.5–7.0, and concentration of aluminon; 1×10−6 M. The linear range of uranium(VI) and zinc(II) were observed over the concentration range 2–33 and 30–120 ng ml−1, respectively. The detection limit (S/N=3) are 0.2 ng ml−1 (uranium) and 30 ng ml−1 (zinc). A good reproducibility shows RSDs of 2.5–4.0% (n=10). The procedure offers high selectivity, with the presence of urea masking some metal ions. 相似文献
973.
[reaction: see text] An efficient method for the preparation of 3-aminofuran-2-carboxylate esters has been developed. This method is based on the reaction of an alpha-cyanoketone with ethyl glyoxylate under Mitsunobu conditions to produce a vinyl ether in good yield. Subsequent treatment of the vinyl ether with sodium hydride afforded the 3-aminofuran. It was also found that a one-pot procedure using the Mitsunobu reaction followed by cyclization afforded the 3-aminofuran in comparable yield. Currently, this method is limited to the synthesis of 5-alkyl-, 5-aryl-, and 4,5-fused bicyclic furans. 相似文献
974.
Gary W Caldwell John A Masucci Mary Evangelisto Robert White 《Journal of chromatography. A》1998,800(2):1071-169
Chromatographic retention factors (k′) of a series of eight β-adrenoceptor antagonist compounds (β-adrenolytic drugs) were determined employing an immobilized artificial membrane column (IAM.PC.DD). The influence of mobile phase pH, ionic strength, and organic modifier composition was studied in order to examine column performance. After the IAM.PC.DD columns were exposed to approximately 7000 column volumes of a 0.01 M PBS mobile phase, five out of six columns tested showed significant peak broadening and decreased k′ values indicative of premature column failure. The data suggested that the immobilized phospholipids stationary phase was removed by the 0.01 M PBS mobile phase. The β-adrenolytic drug's log k′IAM values obtained with an IAM.PC.DD column were compared to an esterIAM.PC.MG column for predicting drug membrane interactions. For the linear regression analysis between log k′IAM and the logarithm of the n-octanol–water partition coefficients (rIAM.PC.DD=0.8710 vs. rIAM.PC.MG=0.9538), the C18 HPLC retention factors (rIAM.PC.DD=0.8408 vs. rIAM.PC.MG=0.9380), the liposome partition coefficients (rIAM.PC.DD=0.8887 vs. rIAM.PC.MG=0.9187), and various pharmacokinetic parameters, significantly better correlations were obtained with the esterIAM.PC.MG column than the IAM.PC.DD column. 相似文献
975.
The filtration performance of yeast cell harvesting was greatly improved by using an oscillatory flow mixing technique in both tubular and flat sheet membrane systems; flux increases of several fold were achieved. The effects of various operating parameters such as frequency, amplitude and ratio of net forward flow rate to oscillatory flow rate were investigated. A simple alternative to the dual head pump, which involved the use of solenoid valves for producing flow reversal, was developed. The flux was significantly increased using this new operating mode. As the only increase of power consumption was from inertia loss due to change of flow direction the additional power consumption is minimal. 相似文献
976.
Chiral molecules that self-assemble to form chiral supramolecular structures exhibit interesting structural features reminiscent of tertiary and quaternary structures of proteins and have applications in catalysis and nonlinear optics. Often, these structures are hierarchical, with their chiral structure difficult to interpret on the molecular scale. In this communication, we observe chiral assembling molecules that form well-defined helices with a pitch of 28 nm. We observe the behavior in both R- and S-enantiomers of the molecule, forming mirror image nanostructures. The molecular chirality is determined by the dimethyloctyl alkyl coil of the molecule and is located more than 4 nm from the hydrogen-bonding segment. The nanostructures observed are not hierarchical, which could be a result of the significant separation between the stereocenter and hydrogen-bonding dendron. The subtle structural modification at the periphery of the molecule biases the supramolecular assembly, which is driven primarily by strong hydrogen-bonding and pi-pi stacking interactions. 相似文献
977.
978.
Three new serratanes were isolated from the nonsaponifiable fraction of western white pine ( Dougl.) bark. The compounds were shown to be 3β-methoxyserrat-14-ene-21α,30-diol (), 3β-methoxyserrat-14-ene-21α, 29-diol (), and 3β-methoxyserrat-14-ene-21β,30-diol (), by a combination of chemical, and spectral methods. 相似文献
979.
Burford N Cameron TS Clyburne JA Eichele K Robertson KN Sereda S Wasylishen RE Whitla WA 《Inorganic chemistry》1996,35(19):5460-5467
The phosphadiazonium cation [MesNP](+) reacts quantitatively with the fluorenylide anion, MesNH(2), and MesOH (Mes = 2,4,6-tri-tert-butylphenyl), resulting in formal insertion of the N-P moiety into the H-Y (Y = C, N, O) bonds. Specifically, reaction of MesNPCl with fluorenyllithium gives the aminofluorenylidenephosphine [crystal data: C(31)H(38)NP, monoclinic, P2(1)/c, a = 9.568(8) ?, b = 24.25(2) ?, c = 11.77(1) ?, beta = 101.38(8) degrees, Z = 4]. Similarly, reaction of [MesNP][GaCl(4)] with MesNH(2) gives the diaminophosphenium salt [MesN(H)PN(H)Mes][GaCl(4)] [crystal data: C(36)H(60)Cl(4)GaN(2)P, monoclinic, C2/c, a = 24.921(2) ?, b = 10.198(4) ?, c = 16.445(2) ?, beta = 93.32(1) degrees, Z = 4], and reaction with MesOH gives the first example of an aminooxyphosphenium salt [MesN(H)POMes][GaCl(4)]. It is proposed that the reactions involve nucleophilic attack at phosphorus followed by a 1,3-hydrogen migration from Y to N. Experimental evidence for the formation of sigma-complex intermediates is provided by the isolation of [MesNP-PPh(3)][SO(3)CF(3)] [crystal data: C(37)H(44)F(3)NO(3)P(2)S, triclinic, P&onemacr;, a = 10.663(1) ?, b = 19.439(1) ?, c = 10.502(1) ?, alpha = 103.100(7) degrees, beta = 113.311(7) degrees, gamma = 93.401(7) degrees, Z = 2]. As part of the unequivocal characterization of the aminooxyphosphenium salt, detailed solid-state (31)P NMR studies and GIAO calculations on the phosphenium cations have been performed. Contrary to popular belief, the phosphorus shielding in dicoordinate cations is not caused by the positive charge but results from efficient mixing between the phosphorus lone pair and pi orbitals. 相似文献
980.
T. Paryjczak J. M. Farbotko K. W. Jówiak 《Reaction Kinetics and Catalysis Letters》1982,20(1-2):227-231
Temperature-programmed reduction and oxidation of bimetallic catalysts Pd–Ni/Al2O3 seem to indicate phase segregation of palladium and nickel oxides and alloying of palladium and nickel in the process of reduction of oxidized catalysts.
- Pd–Ni/Al2O3 , .相似文献